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When Does a Supramolecular Synthon Fail? Comparison of Bridgehead-Functionalized Adamantanes: The Tri- and Tetra-amides and Amine Hydrochlorides

  • Ishtvan Boldog*
    Ishtvan Boldog
    Institute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany
    *E-mail: [email protected]
  • Guido J. Reiss
    Guido J. Reiss
    Institute of Inorganic Chemistry and Structural Chemistry, Heinrich Heine University Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany
  • Kostiantyn V. Domasevitch
    Kostiantyn V. Domasevitch
    Inorganic Chemistry Department, Taras Shevchenko National University of Kiev, Vladimirskaya Street 64, Kiev 01033, Ukraine
  • Tomas Baše
    Tomas Baše
    Institute of Inorganic Chemistry, The Czech Academy of Sciences, v.v.i. 250 68 Husinec-Řež, c.p. 1001, Czech Republic
    More by Tomas Baše
  • , and 
  • Stefan Bräse
    Stefan Bräse
    Institute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany
    Institute of Toxicology and Genetics, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany
Cite this: Cryst. Growth Des. 2019, 19, 9, 5218–5227
Publication Date (Web):July 12, 2019
https://doi.org/10.1021/acs.cgd.9b00594
Copyright © 2019 American Chemical Society

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    Abstract

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    1,3,5-Trisubstituted adamantane carboxamide and amine hydrochloride, Ad(CONH2)3·2.5H2O and [Ad(NH3)3]Cl3·H2O (Ad = adamant-n-yl) respectively, crystallized from aqueous solutions, possess crystal structures with predictable H-bonded assembly, consistent with the C3v symmetry of the building blocks. The triamide structure consists of interpenetrated hexagonal networks, sustained by the well-known cyclic H-bonded bis-amide synthon, R22(8), which ensures linear connectivity. The structure of the triamine hydrochloride, assembled through the tetrahedral {RN+H3···(Cl)3} synthon, features a remarkably symmetric assembly with narrow trigonal pore channels, hosting water molecules. The structures of the tetrahedral 1,3,5,7-tetrasubstituted Ad(CONH2)4 and [Ad(NH3)4]Cl4, obtained similarly, demonstrate a formal prediction failure of synthon-based approach. Instead of the anticipated bis-amide synthon-based diamond network (1.485 g cm–3) analogous to the 5-fold interpenetrated paradigmatic structure of Ad(COOH)4, a non-interpenetrated assembly, sustained by a dense network of H-bonds, is realized (1.433 g cm−3). Lessened geometric regularity was also found in the tetrahydrochloride salt assembled via 5-connected nodes, {RN+H3···(Cl)4}, which involve a bifurcated H-bond. The failures of the supramolecular synthons in these simple cases could be interpreted in terms of either symmetry and/or limitations associated with the “synthon density”. A potential machine-learning approach oriented on heuristic retro-supramolecular synthesis relies on such selected high-weight conceptual cases.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.9b00594.

    • IR spectra (ZIP)

    • Description of the organic syntheses; NMR, IR (also as separate files) and MS spectra; complete single crystal XRD data; powder XRD data; discussion on the structural model of the hypothetic 2-dia structure; topological analysis output (PDF)

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    CCDC 19080471908051 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Cited By

    This article is cited by 3 publications.

    1. Misaki Okayasu, Toshiki Sunakawa, Mitsuru Ikeda, Takaya Namikawa, Riho Hagura, Shoko Kikkawa, Hidemasa Hikawa, Isao Azumaya. Size and Shape Manipulation of Channel Structures Assembled Via Saddle stacking of Tetrapodal Adamantanes Containing Aryl Butadiynyl Moieties. ChemistrySelect 2021, 6 (46) , 13336-13341. https://doi.org/10.1002/slct.202103077
    2. Donglin Shang, Ruide Xue, Lixia Ling, Junping Han, Aihong Li, Nan Yang, Baojun Wang, Jianping Guo, Shengdi Bai. Additional reaction and mechanism of dicyanobenzene: Formation of amidinium or amidine compounds. Journal of Molecular Structure 2021, 1234 , 130203. https://doi.org/10.1016/j.molstruc.2021.130203
    3. E. A. Ivleva, A. I. Morozova, I. D. Suchilin, A. K. Shiryaev, Yu. N. Klimochkin. Synthesis of Substituted Bridged Carboxylic Acids of the Adamantane Series. Russian Journal of Organic Chemistry 2020, 56 (8) , 1399-1406. https://doi.org/10.1134/S1070428020080102

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